Polynuclear aromatic hydrocarbon degradation by heterogeneous reactions with N2O5 on atmospheric particles

The degradation of particulate polynuclear aromatic hydrocarbons (PAH) on atmospheric soot particles in the presence of gas phase dinitrogen pentoxide (N₂O₅) was explored. Dilute diesel and wood soot particles containing PAH were reacted with∼10ppm of N₂O₅ in a 200 ℓ continuous stirred tank reactor (CSTR). To provide a stable source of particles for reaction in the CSTR, diesel or wood soot particles were injected at night into a 25 m³ Teflon outdoor chamber. The large chamber served as a reservoir for the feed aerosol, and the aerosol could then be introduced at a constant flow rate into the CSTR. PAH-N₂O₅ heterogeneous rate constants for wood soot at 15°C ranged from2 × 10⁻¹⁸to5 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. For diesel soot the rate constants at 16°C were higher and ranged from5 × 10⁻¹⁸to30 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. Comparisons with other studies suggest that sunlight is the most important factor which influences PAH decay. This is followed by ozone, NO₂, N₂O₅ and nitric acid. The rate constants of nitro-PAH formation from a parent PAH and N₂O₅ were of the order of1 × 10⁻¹⁹−1 × 10⁻¹⁸ molecules⁻¹s⁻¹. The uncertainty associated with all of these rate constants is± a factor of 3. Given, however, the small magnitude of the rate constants and the low levels of N₂O₅ present in the atmosphere, we concluded that PAH heterogeneous reactions with gas phase N₂O₅ degrade particle-bound PAH or to form nitro-PAH from PAH arenot very important. (Direct application of the specific rate constants derived in this study to ambient atmospheres should not be undertaken unless the ambient particle size distributions and chemical composition of the particles are similar to the ones reported in this study.)     

Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296±2 K

The rate constants for the gas-phase reactions of sabinene and camphene, two monoterpenes emitted from vegetation, with OH and NO₃ radicals and O₃ have been determined at 296±2 K and one atmosphere total pressure of air. The OH and NO₃ radical reaction rate constants were determined using relative rate techniques. Using rate constants of k(OH + isoprene) = 1.01 × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, k(NO₃ + trans-2-butene) = 3.87 × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ and k(NO₃ + 2-methyl-2-butene) = 9.33 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, the following OH and NO₃ radical reaction rate constants (in cm³ molecule⁻¹ s⁻¹ were obtained: OH radical reaction; sabinene, 1.17 × 10⁻¹⁰ and camphene, 5.33 × 10⁻¹¹; NO₃ radical reaction; sabinene, 1.01 × 10⁻¹¹, and camphene, 6.54 × 10⁻¹³. The absolute O₃ reaction rate constants determined were (in cm³ molecule⁻¹ s⁻¹ units): sabinene, 8.07 × 10⁻¹⁷, and camphene, 9.0 × 10⁻¹⁹. These rate constants are compared to literature data for other structural-related alkenes and monoterpenes.     

Heterogeneous transformation of peroxyacetylnitrate

The heterogeneous decomposition of peroxyacetylnitrate (PAN) has been investigated using a flow reactor and infrared spectroscopic analysis. The decomposition rate in air due to glass surfaces follows the relation d[PAN]/dt = −S/V([PAN] × 7 × 10⁷ + [CH₃C(O)OO] × 5 × 90¹²)exp(−9382/T) molecules cm⁻³ s⁻¹ (S/V=surface to volume ratio). The rate observed for NH₄HSO₄-covered surfaces is lower than in the glass case. The rate is high enough to affect many laboratory experiments but too slow to have any influence on PAN decomposition under ambient conditions.     

富营养化水体中光学活性物质的垂向分布及其对遥感反射光谱的影响

富营养化水体中光学活性物质的垂向分布对水下光场分布具有重要影响,决定了水色参数定量遥感反演的精度.基于2011年8月和11月在太湖进行的垂直分层采样,分析了水体中光学活性物质含量的垂向分布特征,并探讨了其影响因素及其对水体遥感反射光谱的影响.结果表明,风速是影响富营养化水体中光学活性物质垂向分布的重要因子之一.风速较小(小于3.0 m·s~(-1))或无风时,表层叶绿素a浓度急剧增加,易形成水华;而风速大于5.0 m·s~(-1)时,水体发生垂直混合,底层叶绿素a浓度最大;其它风速条件下,叶绿素a浓度在某一水深处出现极大值.在风速小于5.0 m·s~(-1)的情况下,悬浮物浓度和有色溶解有机物(CDOM)的垂向分布相对均一;当风速超过5.0 m·s~(-1)时,底泥再悬浮过程对两者的贡献较大.在未发生藻华情况下,0~0.5 m水深范围内的叶绿素a浓度均值与波段比值的相关系数最大(r=0.86),对水体遥感反射比的影响较大;而表层悬浮物浓度对水体遥感反射比的影响最大,研究结论可为水色参数含量的精确估算提供方法论支持.     

1957-2009年黄土高原地区风速变化趋势

用88个气象站1957-2009年的月平均风速和最大风速日值资料,采用距平累积法、 5 a趋势滑动法、 Mann-Kendall趋势检验法等分析了黄土高原地区风速的变化趋势及其空间分异等特征。结果表明:①黄土高原地区1957-2009年多年平均风速为2.36 m/s,水蚀区、 水蚀风蚀交错区和风蚀区年均风速分别为2.36、 2.17、 2.60 m/s,年际变化倾向率分别为-0.008 4、 -0.009 4和-0.018 8 m·s^-1·a^-1,并均通过了0.001的极显著性检验。3个区域均是冬、 春季的平均风速对全年趋势演变贡献率较大,年均风速也均在1981年发生偏强转为偏弱的跃变,20世纪70年代以后平均风速逐渐减小。②黄土高原平均风速减少的主要原因是最大风速为5级或5级以上的发生日数减少。大风频率从1970年代至2000年代呈显著减少趋势,风蚀区减少幅度最大,减少了10%以上,水蚀风蚀交错区减少1%~5%,到2000年代,大多数站点的大风频率均降低为<2%。③水蚀风蚀交错区和风蚀区年均大风日数较多,而水蚀区和黄土高原西部地区年均大风日数较少。根据大风年均发生日数,将大风天气划分为大风天气较少区(年均大风日数<10 d)、 较多区(10~50 d)、 多发区(50~100 d)和频发区(>100 d)。大风较多区在黄土高原地区分布最广,其次是较少区,无频发区。70年代至90年代,风蚀区和水蚀风蚀交错区的站点大多为大风较多区,其中70年代中宁和包头为大风多发区;2000年代以后,大部分地区转为大风较少区。     

京津冀地区重污染天气过程的污染气象条件数值模拟研究

通过采用全球再分析格点资料的统计分析和WRF中尺度数值模拟,从天气学和大气边界层气象学角度分析了2013年12月和2014年2月两次重污染过程中京津冀地区天气尺度大气停滞气象条件和大气污染扩散气象条件的特征及其作用,并根据WRF模式精细化模拟结果分析了太行山和燕山对京津冀地区城市大气污染形成的作用.研究结果表明,两次重污染天气过程中京津冀地区500 h Pa等压面上的平均风速均表现为明显的气候异常特征,500 h Pa平均风速较近10年同期分别下降了约30.8%和50.4%,大气停滞系数较近5年同期分别偏高10%和20%以上;京津冀地区发生严重污染时,WRF模式模拟的日平均混合层高度低于200 m,日平均地面10 m风速低于2 m·s-1,日平均通风量可降低到1000 m2·s-1以下,空气质量指数与日平均通风量成负相关,重污染期间的平均通风量比近5年同期平均通风量偏低29.3%~52.8%,这些不利于污染扩散的天气条件持续数日,导致了重污染天气的发生.此外,太行山对西风气流的阻挡是河北中南部地区大气污染加剧的一个重要原因,而当主导风向为偏南风时,偏南气流遇燕山后或转向回流、或爬坡,导致近地面风速减小,不利于污染物扩散,亦加剧了京津冀地区中南部城市的大气污染.     

Removal of reactive gases at indoor surfaces: Combining mass transport and surface kinetics

The rate of deposition of reactive gaseous pollutants onto indoor surfaces is examined, taking into account mass transport processes and the kinetics of gas-surface interactions. A conceptual model for predicting indoor deposition velocities is proposed, and approximate analysis based on this model is used to obtain algebraic expressions for the deposition velocity of reactive gases under three model airflow conditions: (1) forced laminar convection parallel to a flat plate, (2) laminar natural convection flow along an isothermal vertical plate, and (3) homogeneous turbulence in an enclosure. Numerical simulations are used to refine the approximate analysis results and to predict reactive gas deposition under laminar natural convection flow in an enclosure. The kinetics of gas-surface interactions are modeled in terms of the reaction probability γ, defined as the fraction of pollutant molecular collisions with a surface that result in irreversible removal. Values of γ for the reaction of ozone with surfaces are obtained from published reaction chamber and tube penetration experiments. For common indoor materials, values range from as low as O(10⁻⁷) for glass and aluminium to O(10⁻⁵–10⁻⁴) for materials such as bricks, concrete and latex paint. Our results indicate that ozone deposition occurs at the transport-limited rate when γ > − 3 × 10⁻⁴ for typical indoor air flow conditions, and that ozone deposition can be predicted by surface kinetics alone if γ < ∼ 5 × 10⁻⁷.     

风浪扰动对太湖水体中砷在水相-悬浮物相之间分配的影响

在太湖冬季不同风速下(0.8、1.8、2.7、3.2、4.0 m·s-1)采集了不同深度(水深0.1、1.0和1.8 m,分别记为上、中和下层)的水样,测定了水体和悬浮物中的砷含量及水质参数,计算了砷在两相之间的分配系数,以期了解在太湖生物活动最低的阶段,风浪扰动作用对砷在水相和悬浮物相之间分配的影响.结果显示,随着风浪作用的加强,水体总砷含量有所增加,相应的悬浮物总砷含量及砷的分配系数降低,说明风浪作用可以降低悬浮物吸附砷的能力,以至于促进砷从悬浮物中的释放,进而使水体中的溶解态砷增加.相关性分析及变化趋势比较分析发现,砷分配系数的降低与在风浪扰动的影响下悬浮物浓度和溶解氧的增加,以及叶绿素a浓度的下降有关.不同风速下各参数的垂向分布变化显示,风浪扰动对中下层的砷分配系数以及中层的悬浮物砷含量影响较大;风速变大时,中层溶解态砷含量升高,上层与下层溶解态砷含量降低;而风浪扰动作用对水体总砷的分层变化影响不大.悬浮物浓度、砷浓度及分配系数均在3~4 m·s-1风速下发生变化,且呈现与之前不同的分层特征.4 m·s-1可能是一个临界风速,在4 m·s-1以上的风速下风浪占主导作用,而4 m·s-1以下是湖流与风浪共同作用的结果.     

Wind tunnel simulation of airflow and pollutant diffusion over complex terrain

A wind tunnel simulation of airflow and pollutant diffusion has been conducted for Mt. Tsukuba, a rather isolated mountain. the wind tunnel simulation was carried out in the Thermally Stratified Wind Tunnel of the National Research Institute for Pollution and Resources. The scale of the topographic model was 1/7500 for the horizontal and 1/5000 for the vertical. A nocturnal inversion was simulated in the wind tunnel by heating the airflow to 40°C and chilling the floor of the test section at 10°C. The wind tunnel free stream speed was 0.5 m s⁻¹. The airflow was found to be satisfactorily simulated in the wind tunnel.The upstream flow stagnation, the dividing streamline and the wake in the lee of the mountain were reproduced.     

Precision of the radiochemical OH measurement method

Twenty-eight radiochemical ¹⁴C tracer measurement of tropospheric hydroxyl radical (OH) concentrations were obtained at a rural site near Washington State University, Pullman, WA (117°W, 47°N). Diurnal OH concentration variations were observed for the five days between 9 August and 14 August 1990. These data made it possible to estimate the midday precision and detection limit of the radiochemical OH measurement method. Experiments performed at a peak O₃ photolysis rate J (O(¹D)) of (3.0±0.2) × 10⁻⁵ s⁻¹ yielded a mean midday OH concentration of (5.6±0.1 (1σ)) × 10⁶ cm⁻³. Other data put an upper bound of 16% on fluctuations of instrument sensitivity. Low-light or nighttime background OH concentrations were less than (2.6±2) × 10⁵ cm⁻³. A lower detection limit of 10⁵ cm⁻³ was obtained when extra care was taken with the low-level ¹⁴C counting procedure.     

Building wake dispersion at an Arctic industrial site: Field tracer observations and plume model evaluations

Ten multi-hour atmospheric dispersion SF₆ tracer experiments were conducted during October and November of 1987 near a large oil gathering facility in the Prudhoe Bay, Alaska, oilfield reservation. The purpose of this study was to investigate dispersion under arctic conditions and in situations where building-generated airflow disturbances dominate downwind distributions of ground level pollutant concentrations. This was accomplished with a network of micrometeorological instruments, portable syringe tracer samplers, continuous tracer analyzers, and infrared visualization of near source plume behavior.Atmospheric stability and wind speed profiles at this arctic site are influenced by the smooth (surface roughness = 0.03 cm), snow covered tundra surface which receives negligible levels of solar isolation in winter. The dispersion of pollutants emitted from sources within the oil gathering facility, however, is dominated by the influence of nearby buildings when high winds generate elevated ground level concentrations. An order of magnitude increase in maximum ground level concentration was observed as wind speeds increased from 5 to 8 m s⁻¹ and another order of magnitude increase was observed as winds increased from 8 to 16 m s⁻¹. Variation in maximum concentrations was also observed with changes in wind direction. Vertical plume diffusion (σ_z) near the buildings was a factor of 2–3 greater than that observed in open terrain and was dependent on both wind speed and the projected building width and location of nearby buildings. Wind tunnel tracer distributions for east winds agree with field observations but also indicate that a significant increase in plume downwash occurs with other wind directions. Concentration distributions were calculated using several versions of the Industrial Source Complex (ISC) model. Model estimates of ground level concentrations were within a factor of three depending on wind direction. The model predictions are extremely sensitive to the ratio of plume height to vertical plume diffusion which is significantly influenced by a complex aerodynamic wake in the field.     

Measurements of wind speed and plume rise with a rapid-scanning Lidar

A series of 30-min means of plume rise and dispersion parameters were measured at Fawley power station on Southampton Water between May and December 1989 using a rapid-scanning Lidar. Where possible, plume parameters were determined at three distances, typically 250, 750 and 1500 m, from the stack. Simultaneous measurements of temperature profiles were made using model aircraft and of wind speed and direction using a cup anemometer and wind vane at a height of 44 m on a transmission tower. By matching time series of plume heights at different distances, absolute measurements of wind speed at plume height could be made. These measurements gave a more reliable estimate of plume rise than did surface wind speeds. It was found that, for travel distances out to 1.5 km, the Briggs formula gave a robust prediction of plume heights with C₁ = 1.38±0.07 (95% confidence limits). At Fawley, the standard error in the predicted plume height at 500 m was then 21.0 m, or 19% of the 30-min mean plume rise. For plume-level winds of less than 20 m s⁻¹, analysis of the dependence of plume height on distance, wind speed and power-station load gave a virtual source height of 195.2±10.3 m (95% confidence limits). This is identical with the physical stack height of 198.1 m.     

浅水湖泊水动力过程对藻型湖区水体生物光学特性的影响

基于2010年7月底至8月初对太湖藻型湖区梅梁湾沿岸带水域不同风速条件下水下光场的原位连续高频观测,通过对水下辐照度、光束衰减系数、吸收系数、相关理化参数及气象水文参数的测定与分析,揭示了该区域水体的生物光学特性变化及其与水动力过程的关系.结果表明,总颗粒物吸收系数ap(440)、非色素颗粒物吸收系数ad(440)、浮游植物吸收系数aph(440)及有色可溶性有机物吸收系数aCDOM(440)在小风(30 min内平均风速<3 m.s-1)、中风(3 m.s-1<风速<5 m.s-1)和大风(风速>5 m.s-1)作用下分别为3.97、3.97、6.58 m-1;1.69、2.17、4.20 m-1;2.28、1.80、1.33 m-1;1.05、1.04、1.08 m-1,其中变幅最大的为非色素颗粒物,CDOM吸收系数在不同风速条件下差别不大.水体各组分在PAR波段积分值的贡献率的变化规律为:小风速下浮游植物吸收系数的贡献最大(达42.5%),随着风速的增大,CDOM、浮游植物、纯水吸收系数的贡献率均有降低的趋势,而非色素颗粒物的贡献率则显著增大,分别为33.0%、41.7%、52.0%.PAR漫射衰减系数与10min平均风速呈显著线性相关,风速引起的沉积物再悬浮对PAR漫射衰减系数的影响显著,从小风到大风,PAR漫射衰减系数增加了80.0%,对应真光层深度降低了42.2%.PAR漫射衰减系数、750 nm波长处的光束衰减系数、总悬浮物浓度与风速、波高、波切应力均存在显著正相关,其中又以PAR漫射衰减系数的相关性最为显著.高频观测结果揭示了浅水湖泊藻型湖区水动力过程通过引起沉积物再悬浮、浮游植物的混合及迁移显著改变水体生物光学特性短期变化.     

基于风廓线仪等资料的珠江三角洲污染气象条件研究

利用珠江三角洲区域空气质量资料和珠海、南沙、增城的逐30 min风廓仪观测资料,以及清远探空站每天08时和20时的温度探空资料等,研究了2012年10月珠江三角洲出现的大范围持续性污染天气期间的大气边界层特征.结果表明:2012年10月珠江三角洲出现的大范围持续性污染天气主要是受到弱冷空气南下和台风外围下沉气流天气形势的影响;在污染日,增城、南沙和珠海低层风速普遍小于3 m·s-1,300m高度以下风速甚至小于2 m·s-1,增城和珠海观测站的通风量普遍小于5000~6000 m2·s-1;非污染日的通风量则远远大于污染日;在近海的南沙站和珠海站,海陆风等局地环流的的作用不利于污染物的扩散,海风约出现于下午6时,最大影响高度约600~800 m;逆温层是导致重污染的天气的重要原因,清远探空站频繁出现逆温层,甚至出现多层低空逆温,污染日的逆温层平均厚度和平均强度都较大.     

污水管道增强通风作用下氧气气液传质特性

污水管道的厌氧环境是诱发H2S和CH4等有毒有害气体产生的主要原因,结合我国污水收集系统内建筑排水立管与市政污水管道之间设置化粪池加剧了污水管道通风不畅的现状,提出将建筑排水立管与污水管道直连形成的增强通风系统能够有效提高污水管道通风量,来改善管道气相空间环境.在此基础上,结合实验和计算流体动力学(CFD)仿真方法,以...     

Analysis of atmospheric ozone measurements over a pine forest

Vertical and horizontal profiles of ozone concentration have been measured within the atmospheric boundary layer over the pine forest located in the southwest of France (Landes Forest). Evidence for an ozone depletion in lower layers is obtained from the analysis of vertical profiles recorded at the end of the night. In terms of deposition at the upper canopy level, this corresponds to a disappearance rate ranging between 0.2 and 0.5 cm s⁻¹. The horizontal profiles obtained at midday reveal that ozone vanishes at a rate of the order of 5 × 10⁻⁵ ppb m⁻¹ when air mass moving in the advection direction passes over the forested area. These results are consistent with those obtained by numeric simulation in the case of low emission rates of nitrogen oxides. On the basis of these measurements, the expression of the ozone budget within the atmospheric boundary layer is discussed and compared with the data obtained from the simulation study.     

Real-time,in situ measurements of atmospheric optical absorption in the visible via photoacoustic spectroscopy—IV. Visibility degradation and aerosol optical properties in Los Angeles

Aerosol light absorption (b_abs) has been measured in real-time in Los Angeles with a validated photoacoustic technique, and its impact on visibility degradation has been examined. These measurements were collected during ten days in the summer of 1987 for the Southern California Air Quality Study (SCAQS). Aerosol b_abs (λ = 514.5 nm) varied from an hourly average value of 7 × 10⁻⁶ m⁻¹ in the 3–4 and 4–5 a.m. periods of 13 July to 9 × 10⁻⁵ m⁻¹ in the 7–8 a.m. period of both 28 August and 3 September. This b_abs, which is due solely to elemental carbon (EC) showed a distinct diurnal pattern with low values at night, increasing around sunrise to higher values through mid-afternoon. Comparison of these data with aerosol light scattering data clearly illustrates that the contribution of aerosol light absorption to visibility degradation increases in importance under less polluted conditions. Other urban and rural studies show similar results.     

煤燃烧超细颗粒物的粒径分布及数浓度排放特征试验

利用快速迁移率粒径谱仪(fast mobility particle sizer,FMPS)对煤燃烧排放的超细颗粒物粒径分布特征进行测量研究,并对单位质量煤粉燃烧产生的超细颗粒物数量排放因子进行分析.结果表明,煤燃烧超细颗粒物数浓度粒径谱呈对数双峰分布,颗粒几何平均粒径(the geometry mean diameter,GMD)约为23.1 nm.在燃烧阶段,煤燃烧超细颗粒物数浓度随时间呈指数增长,各模态颗粒物数浓度与煤粉量呈线性相关关系,单位质量煤粉燃烧产生的核模态颗粒物数量排放因子为(1.50±0.64)×1010个·mg-1,爱根核模态颗粒为(1.18±0.56)×1010个·mg-1,积聚模态颗粒物为(0.19±0.06)×1010个·mg-1,总颗粒物为(2.87±1.09)×1010个·mg-1.在扩散过程中,颗粒粒径随时间呈线性增长,粒径增长速率与煤粉量呈线性相关关系.单位质量煤粉燃烧排放的颗粒粒径平均增长速率为7.5 nm·h-1·mg-1.     

气升流速变化对SBR污泥颗粒化的作用及机理

采用两个相同的SBR反应器:R1保持恒定气升流速3.0 cm·s~(-1),R2气升流速由3.0 cm·s~(-1)逐渐降低至1.0 cm·s~(-1),对比研究了气升流速变化对絮体污泥凝聚和颗粒化的作用.结果表明:R1中35 d后絮体污泥全部转变成均值粒径为564.59μm的颗粒污泥;R2中24 d后絮体污泥全部转变成均值粒径978.71μm的颗粒污泥.R2气升流速由3.0 cm·s~(-1)逐渐降至2.0 cm·s~(-1)时,污泥的分形维数(D2)增大;气升流速由2.0cm·s~(-1)逐渐降到1.6 cm·s~(-1)时,D2先下降后上升,污泥粒径比增长率为0.16±0.01,微生物颗粒表面所受的剪切解吸附率随粒径的增长由调整前的1.35×10~(-2)mg·cm~(-2)·d~(-1)(以VSS计,下同)略微降低后升高至1.88×10~(-2)mg·cm~(-2)·d~(-1),颗粒结构变得更加致密;气升流速小于1.6 cm·s~(-1)之后,旋涡尺度作用减弱,D2持续减小.总体上,当气升流速递减后,R2中污泥混合液流变特性发生了变化,形成的漩涡尺度大于R1,促使更多体积分数的污泥分布在漩涡尺度的耗散范围内,加剧耗散对应范围粒径大小的污泥剪切凝聚,加快了污泥颗粒化进程.